Certain water-soluble high molal oxyalkylated esters and method of making same



Patented Nov. 21, 1944 CERTAIN WATER-SOLUBLE HIGH MOL,AL

OXYALKYLAT-ED ESTERS AND METHOD oF MAKING SAME Melvin De Groote,University City, and Bernhard Keiser, Webster Groves, Mo.,- assignors toPetrolite Corporation, Ltd., ,corporation of Delaware Wilmington, DeL, a

No Drawing. Original application July7, 1941, Serial No. 401,381.Divided and this application March 9, 1943, Serial No. 478,592

12 Claims; (c1; zoo-404.5)

This inventionrelates to a new chemical prodnot, our present applicationbeing a division oi our pending application Serial No. 401,381, filedJuly '7," 1941, for Process for breaking petroleum emulsions, whichsubsequently maturedlas U; S. Patent No. 2,324,493, dated July 20, 1943.

One object of our invention is to provide a new chemical product orcompound that is'particularly adaptedfor use as a demulsifier intheresolution of crude oil emulsions.

Another object of our invention is to provide a practicable method formanufacturing said new chemical product or compound.

Althoughaone of the primary objects. of our invention is to provide anew compoundor composition ,of matterthat. is an efficientdemulsifier.for crudeoil emulsions of thewater-in-oil type, the saidcompound or composition of mat .ter may be employed in other arts, ashereinafter indicated.

The new chemical compound or composition of matter herein described isexemplified by the acidic or, preferably, neutral ester derived bycomplete esterification ofone mole of a polyalkyleneglycol ,of the kindhereinafter described, with two moles of a fractional ester derived froma hydroxylated material of thekind herein described, and a polybasiccarboxy acid having not over six carbon atoms.

If ahydroxylated material, indicated for the sake of convenience by theformula TJOH, in .which T .is an-alcohol, residue, is reacted with apolybasic carboxy acid, which, similarly, may .con veniently be ofthedibasic type and indicated by .theformula HOOQDCOOH, in which .Dis adicanboxy acid residue, then the fractional ester obtainedby. reactionbetween equimolar quantities may beindicated bythe following formula:

noodncoom The polyethylene glycol may be characterized by "materials ofthe kind such as heptaethylene glycol, octaethylene glycol, nonaethyleneglycol, decaethylene glycol, to and including heptadecaethylene glycol.For convenience,these polyethylene glycols may be indicated bythefollowing formula: 1

I mH

in which 111. varies from '7 through I? 1 Instead of polyethyleneg1yCO'1S, Oll8.m&y use polypropylene glycols or polybutylene glycols.

Thus, for convenience, in the broadest aspect,

the polyalkylene glycols employed'may be indicated by the followingformula:

OH(C nH2nO) mH in whichrm has its previous significance} and nrepresents a numeral varying from 2 to 4.

Thus, the bulk of the materials herein contemplated may be indicatedwithin certain variations,

ashereinafter stated, by the neutral ester derived b esterification ofone mole of a glycol of the kind above described, with twomcles Ma 'lyabove the boiling point of water.

ethylene glycols.

fractional ester of the kindpreviously described.

The formation of the. compound may be indicat- ,ed by the followingreaction, although obviously it is immaterial What particular procedureis employed to producethe particular chemical com- .pound or product: a

T.OOC.D.COOH+QH'(C2H4O) mH+ As indicated previously, thepolybasic acidsemis usually concerned, largely, with convenience of manufacture of thefinished ester, and also of the price of the reactants. Generallyspeaking, the-higher the temperature employed, the easier it is toobtain large yields of i the esterified product. Although oxalic acid iscomparatively cheap, it. decomposes somewhat readily at slight- For thisreason, it is more desirable to use an acid-which is more resistant topyrolysis. Similarly, when a polybasic acid is available in the form ofan anhy-dride, such. anhydride is apt to produce the ester withgreatercase than the acid itself.

adaptable; and also, everything else considered, the cost iscomparatively low on a per molar basis, even though. somewhat higher ona per pound basis. Succinic acid or the anhydride has many of theattractive qualities of maleic anhy-dride; and this-is also true. ofadipic acid. For purposes of brevity, the bulk of the com- The selectionof For this reason, maleic anhydride is particularly pounds hereinafterillustrated will refer to, the

use of maleic anhydridaalthough it is understood that, any othersuitable polybasic acid may be employed. Furthermore, for purposes ofconvenience, reference is made to the use of poly- As has beenpreviously indicated, such glycols can be replaced by suitablepolypropylene or polybutylene compounds.

As far as the range of oxyalkylated compounds employed as reactants isconcerned, it is our preference to employ those having approximately8-12 oxyalkylene groups, particularly 8-12. oxyethylene groups. Ourpreference to use the oxyethylated compounds is due, largely, to thefact that they are commercially available, and particularly so. in twodesirable forms. The most desirable form is the so-called nonaethylenglycol, which, although consisting largely of nonaethylene glycol, maycontain small amounts of heptaethylene and octaethylene glycols, andpossibly minor percentages of the higher homologs. Such glycolsrepresent the upper range of distillable glycols; and they may beconveniently referred to as upper distillable ethylene glycols.. Thereis no particularly good procedure for making a sharper separation on acommercial scale; and it is understood that mixtures of one or more ofthe glycols may be employed, as well as a single glycol. As pointed out,it is particu larly preferred to employ nonaethylene glycol ascommercially available, although it is understood that this productcontains other homologs, as indicated. s

. Substantially as desirable as the upper distillable polyethyleneglycols, are the lower nondistillable polyethylene glycols. Thesematerials are available in the form of a waxy water-soluble material,andthe general range may vary somewhat from decato tetradecaethyleneglycol.

The hydroxylated compounds employed as reactants in one'mode ofmanufacture of the present compounds are hydroxylated acylated amidescontaining: (a) an amino nitrogen-linked acyl radical derived from amonocarboxy acid having not more than 5 carbon atoms; (1)) an acylradical derived from a detergent-forming monocarboxy acid having atleast 8 and not more than 32 carbon atoms; and (c) an alcoholiformhydroxyl radical.

Detergent-forming acids having at least 8 and not more than 32 carbonatoms are exemplified by fatty acids, naphthenic acids, abietic acids,oxidized parafi'ln or wax acids, or the like, or by simple modificationsthereof which do not detract I from the ability. of the acid to combinewith alto oxidized petroleum acids, see U. S. Patent No.

IAS is well understood, the method of producing such glycols would causesome higher homologs to be formed; and thus, even in this instance,there may be present some oxyethylene glycols within the higher rangeabove indicated. One need not point out that these particular compoundsconsist of mixtures, and that in some in-,

stances. particularly desirable esters are obtained by making mixturesof the liquid nonaethylene glycol with the soft, waxy, lowernon-distillable polyethylene glycols. For the sake of convenience,reference in the examples will be to nonaethylene glycol; andcalculations will be based on a theoretical molecular weight of 414.Actually, in manufacture, the molecular weight of l the glycol employed,whether a higher distillable found it most desirable to react theselected glycol or mixtures of glycols with maleic anhydride in a ratioof two moles of the anhydride for one mole of the glycol. Under suchcircumstances, wehaye found little tendency to form longer chainpolymers; and in fact, the product of reaction, if conducted atreasonably low temperatures, appears to be largely monomeric. Forconvenience, such intermediate fractional ester may then be consideredas a dibasic or polybasic acid. One mole of the intermediate fractionalester, so obtained, is then reacted with two moles of the alcoholicmaterial of the kind subsequently described.

It is to be noted, however, that if one prepares a fractional acidicester, then if two moles of the fractional acidic ester are reacted withone mole of the polyethylene glycol, there is no possibility for theformation of polymeric types of esterification products under ordinaryconditions.

amine,

2,242,837, dated May 20, 1941, to Shields.

Thus, hydrogenated oleic acid, chlorinated naphthenic acid, orbrominated abietic acid will form such detergent-forming bodies with thesame ease as the parent materials themselves. The oxidized acidsobtained by blowing or oxidation of the acids or esters, aresatisfactory. Such acids have frequently been referred to collectivelyin the art as monocarboxy detergent-forming acids. Needless to say, theacylation need not be conducted by means of the acid itself, but may beconducted by means of any compound of the acid which contains the acidradical; for instance, an ester, an amide, an anhydride, an acylchloride,

etc.

It is our preference to use the fatty acids as the most desirable formof a detergent-forming acid, and particularly the unsaturated fattyacids, for instance, ricinoleic acid, oleic acid, mixed fatty acidsderived from soyabean oil, rapeseed oil, sesame oil, cottonseed oil,corn oil, peanut oil, and the like. Fatty acids, such as lauric acid,myristic acid, palmitic acid, and the like, may be employed.

The low molal monocarboxy acids having not more than five carbon atoms,are exemplified by acetic acid, formic acid, lactic acid, propionicacid, butyric acid, hydroxybutyric acid, furoic acid, etc.

In regard to both the detergent-formingacids and in regard to the lowmolal acids, it is obvious that one need not use the acid itself as areactant, but may use some suitable derivative, such as the acylchloride, the anhydride,.the ester, or amide; i. e., any suitable formmay be used which is the functional equivalent in supplying the acylradical.

Suitable primary and secondary amines which may be used as primaryreactants include the following hydroxylated types: diethanolamine,monoethanolamine, ethyl ethanolamine, methyl ethanolamine,propanolamine, dipropanolamine, propyl propanolamine, etc. Otherexamples include cyclohexylolamine, dicyclohexylolamine, cyclohexylethanolamine, cyclohexyl propanolbenzylethanolamine, amine,pentanolamine, hexanolamine, octylethanolamine, octadecylethanolamine,cyclohexanolethanolamine, etc.

If the low molal monocarboxy acid is selected so as to be hydroxylated,as in the instance of glycolic acid, lactic acid, hydroxybutyric acid,and the like, it is obvious that by esterifying a hydroxylateddetergent-forming acid, for instance, ricinoleic acid, hydroxystearicacid, and

' the like, could be esterified therewith, i. e., withbenzylpropanolmolalaacylrnzadical: zonezizcan employ l a :aprimary orsecondary amine which need not be hydroxylated. Under thesecircumstances, one

i might -em-ploy compounds such as *amylarnine,

diamylamine; -b'uty-1amine,--" dibutylamine, 'benzyl- -&

amine, cyclohexylamine, etc.

Other i isuitable types rzOf" y amines -w;ill:- be describedsubsequently. Fob-instances, one may employ the type involving "thepresence of an secondary hydroxylated amines there, described.

Such additional amino compoundsare suitable as reactants, in view ofWhat will 'be said subsequently;

Example A, partl,. --,of :-the aforementioned Cahn and Harris patent,will serve: excellently as an initial illustration and is as "follows:

4 Example-A (1) 224 grams of methyl acetate (3 moles) and 210 grams ofdiethanolamine (2 'moles) were mixed together, two layers .forming atfirst, the mixture becominga homogeneous mass after a :short time. "Themixture "wasrefiuxed for. 19

hours, at Whichtime-90% of the diethanolarnine had reacted. 'Anportion=ofithe -reaction 'mixture was subjected to a vacuumof 6-millimeters"at60 degrees. C. vin order toldrive-ofi the volatile reference ,willbemade to .U; S.

.mole of :suchtdetergenteforming acid with a .com cpound *of itherkindlab'ove described; for the area- :son that "there :must be aresidual alcoholiform hydroXyl radical. If, however, an acid such-.as

;ricinoleic :acid,hydroxystearicacid; or the like .is employed, then, ofcourse, two .moles of :such detergent-forming acid can be employedSimilarly, if desired, one might esterify one'hydroxyl with oleic' acid,land. the other hydroxyl with ricinoleic acid.

If the experiment above described is repeated,

'using monoethanolamine in the equivalent was material, namely, theunreacted methylacetate and the methyl alcoholwhich was formed duringthe reaction. residue zuponititration, showed a:C0ntent'."{Of,4-.J64%,lbfdfree :diethan'olamine. ,To 192;5= grams ofzthis residuefxfi ill grams of methyluzac'etate.werer addedl and'lthemixture was refluxed for 3, /2.hours., The .resulting reaction productwas then freed from its.

low boiling constituentspnamely, the methyl al cchcl and unreacted:methyl acetate, .by :maintaining the mass at '70 degrees zcmunderva'pressure of 6 millimeters. The residue contained approximately 0.8% of'unreacted diethanolamine, based upon a determination of the alkalinityof ,said residue by titration. ,Theproduct was alight yellow coloredsyrup,..soluble,in waten-and :contained a compound which was essentiallythe acetic acid amidepf 'diethanolamine; having the following formula:

.ozmon CHz-G-Y-N (1:0 ClQiHiDH Having obtaineduaa-material of the kindabove described, it is obvious that ,onecan :thenlesterify thematerialwith ,eitherqone .or two. molestof a detergent form'ingmonocarboxy acid, sofas to obtain alhydroxylated derivative. 1Obviously, if

the .detergenteforming acid employed does not contain an. alcoholic,hydroxyl lradical,,.;for, in-

stance, if ituis of the type other :than that exemplified .byHricinoleic acid, uhydroxystearic :acid and the'like, thenkonecan lonly1esterify-;one

.the following:

amount, then the final product is characterized*byathefollowingyformulaz l C2H4OH enro- The limitations-in-regard tothe above type of compound is. perfectlylobvious. 1Unlessfionecanproducer a secondary amide, rwhichtis difficult,

:and, generally speakingynot particularly feasible, --one:must,. ofnecessity;.:esterify"with: a hydroxylfated detergent-forming acid,suchras ricinoleic acid, ,hydroX-ystearic acid,ror 'the like.

If,'however, instead of using acetic acid,=one uses lactic i acid .or'some other hydroxylated low molal carboXy aacid, then the "two formulasabove .described change to :athe following formulas: l

(1211203 oHoHao-n l o wolmon (121L011 (l \H The presence of thisadditional hydroxyl offers additionalopportunity for reaction andfurther elaboration is not necessary, except perhaps, to point outthateven -a"-typeof material such as =m-ight be employedpprovided:thatricinoleic:acid,

for example, isv esterifiedcwith' athe hydroxyl of the low -molalmonocarboxy if acid acyl group.

"Other variants. too numerousto mention suggest themselves, as, :forexample, derivatives :of :tris (hydroxymethyl am'inomethane or similartypes of compounds, such asxanamide of the following type whichmay beused ferreaction with-amdetergent-forming acid:

CHIOH CHa-C-NH-O-OHzOH H CHzOH Another suitable raw material is monogly-,cerylamine, .as indicated by the following formula:

OH ;.I]I[ G;H5/ H \OH Attentionis directed to the aforementioned Cahnand..Har.ris patent,..insofar that it illustrates a large number ofintermediate products which may be utilized to produce various finalcompositions of matter,-as, for example, sulfa-ted orsulfonatedderivati-ves, as contemplatedlinsaid aforementioned U. S.Patent No. 2,238,929) .How-

ever the intermediate materials there described obviously can be used asalcoholic bodies in the preparation of compounds of the type hereincontemplated. Such materials as there described are largely derivativesof hydroxylated secondary amines; but for the purposes hereincontemplated, such limitation does notexist, in view of what has alreadybeen said.

By way of illustration, the following examples will serve:

I-IYDRoxYLATED AMIDE TYPE INTERMEDIATE Example 1 1 One pound mole of anamide of the following I formula: l

is reacted with one pound mole of ricinoleic acid until esterificationis complete. Such esterification reaction can be conducted by any one ofthe conventional means, usually heating at a temperature above theboiling point of water; for

instance, 116-160 C. is sufiicient. In some cases it may be desirable topass a dried inert gas through the reacting mass, as, for example, driedcarbon dioxide or dried nitrogen. Sometimes the reaction is extended bythe .presence of a small amount of a sulfonic acid as a catalyst,-

for instance, of toluene sulfonic acid. In

other instances, esterification may be conducted in the presence of aninert solvent, such as xylene, which is permitted to distil off carrying,'water vapor with it. The vapors are condensed,

separation of water and xylene permitted to take place, and the xylenereturned to the reacting vessel while the water is diverted to asuitable draw-off connection.

HYDRoxYL TED AMIDE TYPE INTERMEDIATE Example 2 51.0 grams (2 moles) ofthe acetic acid amide of diethanolamine, produced as described in part 1hereof, and 38.0 grams (1 mole) of lauric acid were heated together for15 minutes at approximately '200 degrees C., while passing carbondioxide gas through the reaction mixture.

decreased to 1.3%. The product was a yellow colored syrup dispersible inwater and having good foaming properties. It could be salted out of itssolution by the addition thereto of sodium chloride. The productconsisted essentially of a compound having the following formula:

CzHlOH CHz-GN O CzH4-O$IJ-C11H2:4

, HYDROXYLA'IEDYAMIDE TYPE INTERMEDIATE Example 3 A The same procedureis followed as in Example 2, except that ricinoleic acid is substitutedfor lauric acid.

. At the 1 'end of the 15 minutes, the free lauric acid had HYDRoxYLATEDAMIDE TYPE INT R EDIATE Example 4 v The same procedure is followed as inExample 2, except that naphthenic acid is substituted for lauric acid.

HYDRoxYLATE AMIDE TYPE INTERMEDIATE Example 5 v The same procedure isfollowed as in Example 2, except that abietic acid'is substituted forlauric acid in Example 2.

HYDROXYLATED AMIDE TYPE INTERMEDIATE Example 6 The acetic acid amide oftris(hydroxyethyl)- aminomethane, previously described, is substitutedfor the acetic acid amide of diethanolamine,

in Examples 2-5, preceding.

Having obtained hydroxylated acylated amido compounds of the kindpreviously described, the

next step, of course, is to obtain fractional esters derived fromnonaethylene glycol of A the kind described in the earlier part of thepresent disclosure. Such materials may be'illustrated by the following:

GLYCoL EsTER INTERMEDIATE PRODUCT Example 1 One pound mole ofnonaethylene glycol is reacted With two pound moles of maleic anhydride,so as to form nonaethylene glycol dihydrogen dimaleate.

GLYcoL EsTER INTERMEDIA E PRODUCT Example 2 A mixture of lowernon-distillable polyethylene glycols, representing approximately decatotetradecaethylene glycol, is substituted for nonaethylene glycol in thepreceding example. GLYCoI. EsT R INTERMEDIATE PRODUCT Example 3 A 50-50mixture of nonaethylene glycol and lower non-distillablepolyethyleneglycols of the kind described in the previous example is substituted fornonaethylene glycol in Example-l.

GLYCoL EsTER INTERMEDIATE PRODUCT Example 4 Adipic acid is substitutedfor maleic anhydride in Examples 1-3, preceding.

GDYcoL EsTER INTERMEDIATE PRODUCT Example 5 Oxalic acid issubstitutedfor maleic anhydride,

in Examples 1+3, preceding.

GLYCoL ESTER INTERMEDIATE PRODUCT Example 6 Citric acid is substitutedfor maleic anhydride in Examples 1-3, preceding. I 1

GLYCoI. EsTER INTERMEDIATE PRODUCT I Example 7 7 Succinic anhydride issubstituted for maleic anhydride in Examples 1-3, preceding.

The method of producing'such fractional esters is well known. Thegeneral procedure is to employ a temperature above the boiling point ofwater and below the pyrolytic point of the reactants. The products aremixed and stirred constantly during the heating and esterification step.If desired, an inert gas, such as dried nitrogen, or dried;carbonifdi'oxide, may be passed through the mixture; Sometimes it: isdesirable. to add an esterificationw catalyst, such as sulfuric acid;benzene sulfonic acid, or: the-like. 'I-hiszis the sameigeneralprocedure as employed in the manufacture of ethylene" glycol: dihydrogendiphthalateo See U Sr Patent No; 2,075,107, dated MarchBO, 1937,ctoFrasier;

Sometimes i esterification is conducted most readily inthe. presence ofan inert solvent, that ated, such water of esterificationis absent whenthe reaction involves an acid; anhydride; such as maleic anhydride; and-a-glycol.? However, if

Water is formed, for instance, when citric, acid is employed, then asolvent such asxylenemay be present iand employed to carry off the waterformed. The'm-ixture of xylene vapors: and water vapors canhe'condensed"so that the water is separated- The xylene is thenreturnedto the reaction vesselfor further circulation. This isaconventional and. well. known procedure. and requires no furtherelaboration.

COMPOSITION or MATTER Eziiample 1 Two pound moles-of al mater-iale ofthe kind exemplified by Hydroxylatedamide type intermediate, Example 1,preceding, are reacted with one pound mole of a glycol esterintermediate product of the: kind describedunder Glycol esterintermediate: products, Examples 1, 2 and 3, pre-- ceding. Such reactioniscontinued until substantially all carboxyl. acidity has disappeared.The time of reaction may vary "from a few hours to as many as hours; i vi COMPOSITION "orj MATTER Example 2 The same procedure is followedas' inComposition of -matter; Example 1, except that one employs ahydroxylated amide type intermediate product described in- Hydroxylatedamide "type intermediate, Example 2, preceding,- instead ofrin! Example1.

Co PosI'rmN-or Murcia,

Ewample t i ,Thesame procedure is followed as in'Composition ofmatter,Example1, except that one employs -a material of "the kinddescribed in Hydroxylated amide type intermediate; Exam The sameprocedure is followed as in Composition of matter, ,Example 1, exceptthat one employs a materialbf the 'kind described in Hydroxylated amidetype intermediate, Example 5,, preceding, instead of in Example 1;

carriestaway the water of esterification which maybe formed, although,as is readily appreci- COMPOSITION or Marrsn-- Example 6 Thesame-procedure is followed as inComposition of matter, Example 1',except that one employs a material; of the kind described inHydroxylated amide, type; intermediate, Example,

6, preceding; instead oiin Example 1.

Comrosrrroiror MATTER it ample? Glycol ester intermediate products ofthe kind exemplified by Examples 4 7, preceding, are substituted forGlycol intermediate products, Exampies-1,2 and 3, in the preceding 6examples.

Reviewing :what has been said, it is obvious thatawidetrange in, carbon.atom content exists in regard to the alcoholictbodies employed forreaction with the glycol dihydrogen diacid ester. This ,may-beillustrated by considering two examples. If hydroxyacetic acid isreacted .with.

ethylamine or acetic acid with monoethanolamine, the compound soobtained contains4 carbonratomsg -and after reaction withoctanoic acid,

rived from acetic acidiand diethanolaminehas i of th intermediateproduct.

any particular method may be used to produce the-desiredcompounds of thekind indicated. a

thealcoholic body contains a, total of 12 carbon atoms. On the, otherhand the; product i de- 6: carbon atoms, and one can introduce, tworicinoleyl radicals, adding 36 more carbon atoms' Indeed, other; similarderiyativessuggest themselves, whereby three ricinoleyl radicals, areintroduced, thus adding 54 carbon atoms.) The upper carbon atomlimitthen approximates 60,

carbon atoms, or 70 carbonatoms. r h

It is to b noted thatthis second stepis an esterification, reaction,and-the same procedure is, employed as suggested above in thepreparation Needless to say,

In,- some instances it maybe desirable to conduct the esterificationreaction in-the presence of anon-volatile inert solvent which simplyacts asa diluent; or viscosity reducer.

In the preceding examples attention has been, directed primarilyto themonomeric form, or at least, to-the form in which the bifunctionalalcohol, e., a glycol, and the polyfunctional acid,

usuallyabifunctional compound, reactto give a chain type compound,inwhich the adjacent acid and glycolnucleus occur as a structural unit.For instancein the monomeric form this may be indicatedin the followingmanner:

acid 5 glycol acid If, however, one" prepared an intermediate productemployingthe ratio of three moles of maleic anhydride and twomole's ofnonaethylene glycol, th'e tendency wouldbe to produce a prodnot whichmight be indicated in the following manner I v inwhich the charactershave theirprevious sig l acid glycol 1 acidf. .,glycol acid Similarly,three moles of theglycol andfour moles-of theacid might tend to give acombination which maybe indicated thus:

Another 'way of stating the matter isthat the composition maybeindicated in the following ni ficanc'e and a: is a relativelysmallwhole number'less than .10 andj'probablyless than 5; and

stead of adipic acid;and

in the monomericform m, of course, is 1. The limitations on the size ofa: are probably influenced, largely, by the fact that reaction leadingto further growth is dependent upon random contact. I

Some of the products are self-emulsifiable oils, or self-emulsifiablecompounds; whereas, others give cloudy solutions or sols; and the most-desirable type is characterized by giving a clear solution in water,and usually in the presence of soluble calcium or magnesium salts, andfrequently, in the presence of significant amounts of either acids oralkalies.

Water solubility can be enhanced in a number of ways which have beensuggested by previous manufacturing directions, for instance: 1

(a) By using a more highly polymerized ethylene glycol;

(b) By using ,a polymeric form instead of a monomeric form in regard tothe unitwhich forms the chain between the two alcoholic nuclei;

(o) By using apolybasic carboxy acid of lower molecular weight, forinstance, maleic acid in- (d)= By using an alcoholic reactant of lowersheath which remains afterv drilling by the rotary method. Sometimes thedrilling mud contains added calcium carbonate or the like to render themud susceptible to reaction withhyits removal.

drochloric acid orthelike, and thus expedite Chemical compounds of thekind herein described are also of Value as surface tension depressantsin the acidization of calcareous oilbearing'strata by'means of strongmineral acid, such as hydrochloric acid. Similarly,'some membersareeffective as surface tension depressants I or wetting agents in theflooding of exhausted molecular weight, or one having more hydroxlygroups, or possibly, having one or more ether groups.

Indeed, in many instances the hydroxylated body may show some tendencytowards water solubility or self-emulsification prior to reaction with aglycol ester. It is to be noted in this in: stance that the hydroxylatedmaterials which are employed prior to reaction with the glycol ester arelargely of the'water-insoluble type, but in such instances where theyare self-emulsifiable or show hydrophile. properties, they are equallysuitable. I a l 1 Actually, a reaction involving an alcohol and an acid(esterification) may permit small amounts. of either one or both of thereactants, depending upon the predetermined proportion, to remain in anunreacted state. In the actual preparation of compositions of the kindherein contemplated,-any residual acidity can be removed byany suitablebase, for instance, am-

monia, triethanolamine, or the like, especially in dilute-solution.Naturally, precaution should be taken, so that neutralization takesplace without saponification or decomposition of the ester.

Insome cases there is no objection to the pres-' ence of the acidicgroup. Indeed, if a tribasic acid be employedinsuch a. manner as toleave onefree carboxyl group, then it is usually desirable to neutralizesuch group by means of a suitable basic material.

In the hereto appended claims, reference to a neutral product refers toone which free carboxylic radicals are absent.

Materials of the kind herein contemplated may find uses as wetting,detergent, and leveling agents in the laundry, textile, and dyeingindustry; as wetting agents and detergents in the acid washing of fruit,in the acid washing of buildingtstone and brick; as a. wetting, agent,and

spreader in'the application of asphalt in road building and the like,asa constituent of soldering'flux preparations; as a flotation reagent inthe flotation separation of various minerals; for flocculation andcoagulation of various. aqueous suspensions containing negativelycharged-particles, such as sewage, coal washing wastewater, and'varioustrade wastes and the like; as germicides insecticides, emulsifiers forcosmetics,

' ner:

. defined.

of the kind herein described as demulsifiers, or

in particular as surface tension depressants, in combination withmineral acid or acidization of oil-bearing strata, reference is made toU. S. Patent No. 2,233,383, dated February 25, 1941, to De Grooteand-Keiser. v I

It will be apparent to those skilled in the art that residual carboxylacidity can be eliminated by esterification with a low molal alcohol,for instance, ethyl, methyl, or propyl alcohol, by conventionalprocedure, so as to give a substantially neutral product. Theintroduction of such low molal hydrophobe groupsdoes not seriouslyaffect the solubility, and in some instances, gives increasedresistance, to soluble calcium and magnesium salts, for such property isof particular value. Usually, however, neutralization with a dilutesolution of ammonia or the like is just as practicable and lessexpensive.

In the hereto appended claims it is intended that the monomeric formscontemplate also the polymeric forms, insofar that the polymeric formsare nothing more or less than a repetition of the monomeric formsseveral times over, withthe loss of one ormore molesof water.

What has just been said canbe recapitulated and presented in more formalagreement with customary nomenclature in the following man- As statedpreviously in the broadest aspect, the polyalkylene glycols employed maybe indicated by the following formulas in which m has its previoussignificance, and n represents anumeral varying from 2 to 4. In

simpler form this structure can be indicated in the following manner:

m-whicn the divalent radical -RO is the divalent radical (C1i H2tO')m aspreviously The dibasicacid pr viousl referred to in its succession ofthe intermediate steps.

I. [Ha l ps;lam,

2.;363l049.1* simplest form. as HOOCIDzCOOI-I is more? com-1;

pletely portrayedlbythe; following formula:,

coon Re cooH I (G H'MJ in which R1 is the polybasic carboxyacidresidue,"

except in theuni'que case of oxalic, and n" is the numeral "-orl,depending on whether or not the polybasic acid is dibasic or tribasic.

If the polybasic acid just described is indicated by R, and if theglycol just described is indicated by R, then the acidic or fractionalester previously described earlier in thespecification maybe indicatedby the following formula t i in which 12 and p represent numeralsvaryingfrom 1 to 10, and p" represents a numeral varying from 1 to 20, and RfandR have their prior significance, and the ratio ofpto p varies from2:1 to pi-1:40, with the obvious proviso that .such ester must containatleast two free car- Such hydroxylated amide, if obtained from some ofthe reagents previously mentioned, to wit:tris(hydroxymethyl)aminomethane, lactic acid, and ricinoleic acid, wouldcontain as many as five alcoholic hydroxyl radicals.

coholic hydroxyl radical. Thus, the hydroxylated amide hereincontemplated may be indicated by the formula R2(OH)1w in which thehydroxylated acylated amide radical R2 contains (a) An aminonitrogen-linked acyl radical derived from a monocarboxy acid having notmore than 5 carbon atoms;

(5) An acyl radical derived from a detergentforming monocarboxy acidhaving at least 8 and not more than 32 carbon atoms; and l (0) Analcoholiform hydroxyl radical, and n" represents a small whole numbervarying from 1 to 5.

The new composition of matter herein contemplated is best represented asan ester obtained by the esterification reaction involving the acidicfractional ester above described and the hydroxylated acylated amidepreviously depicted in detail. The final composition may be obtained inany suitable manner and would properly represent the final product,regardless of the So portrayed, the structural formula is as follows:

significance, and m. represents a numeral. from.

1to-5,.mf'nepresents:a numeral from 1 to 3;v and.

In other in-v stances, there might be present only a single al-' mfrepresents. a numeral varying. from 1. to. 5;

It has been previously pointed: out that in re,- sidual carboxylicradicals, and especially: one obtained: from tribasictacids, it could beneu-. tralized: with a variety of suitable basic mate.- rials. .In otherwords, a residual carboxylic hydrogen, atom may be replaced by ametallic atom. an ammonium radical or substituted ammonium.

radical, as previously indicated. Under such cir-- cumstances, anyresidual carboxylic. radical, in-- stead-of appearang thus: COOI-I, may,in essence, be theradical COOR3 in which. R3 rep.- resents a cationincluding the acidic hydrogen.

atom. This can'best be disposed of by'rewritingj theformula forpthepolybasic carboxy acid, thus: i T coon Rlc0.0H

i (C'OORaM in which all of the characters have their previoussignificance. i

Having thus described our invention, what we claim as new and desiretosecure by Letters Patent is: i i l 1'.-A water-soluble-ester of theformula:

[[Mm-e; w p l in which it represents the numeral 11 to 5, m representsthe numeral lfto' 3, and m" represents the numeral from 1 to 5; and inwhich 11-.

and p ,represent numerals varying, from, 1 to 10, and the ratio of p to10' varies from 2:1 to p-|l:p, and 15' represents a numeral varying from1 00 20, and R is a glycol of the formula HOROH in which the .divalentradical -RO.- is the divalent radical -(CnH2nO) m in which radical, inturn n represents a numeral in which R1 is the polycarboxic carboxy acidI residue, and R3 represents a cation including the acidic hydrogenatom, and 'n is the numeral 0 or 1; R2(OH)7L" is a hydroxylated acylatedamide in which the acylated amide radical R2 contains (a) An aminonitrogen-linked. acyl radical derived from a monocarboxy acid having notmore than 5 carbon atoms;

(b) An acyl radical derived from a detergentforming monocarboxy acidhaving at least 8 and not more than 32 carbon atoms; and

(0) An alcoholiform hydroxyl radical, and n" represents a small wholenumber varying from 1 to 5.

2. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0.

3. A water-soluble ester, as defined in claim 1, wherein all occurrencesof 11. are 0, and n,represents the numeral 2.

4. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0, n represents the numeral 2, and 112 represents a numeral.varying from 7 to 11.

5. A water-soluble ester, as defined in claim 1,

in. which: all; of the characters: have their prior:

wherein all occurrences of n are 0, n represents the numeral 2, and mrepresents a numeral varying from '7 to 11, and the high molal acylradical which is part of R2 is an 18 carbon atom fatty acid residue.

6. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0, n represents the numeral 2, m represents a numeral varyingfrom '7 to 11, and the high molal acyl radical acid residue, the ratioof p to p'is 2'to 1, and

with added neutralization of all residual acidity. 8. A water-solubleester, as defined in claim 1, wherein all occurrencesof n are 0, nrepresents the numeral 2, m represents a numeral varying from 7 to 11,and the high molala'cyl radical which is part of R2 is a ricinoleic acidresidue, the ratio of p to p is 2 to 1, and with added neutralization ofall residual acidity.

9. A water-soluble ester, as defined in claim 1, wherein all occurrencesof n are 0, n represents the numeral 2, m represents a numeral varyingfrom '7 to 11, and the high molal acyl radical which is part of R2 is aricinoleic acid residue, the ratio of p to p is 2 to 1, withaddedneutralization of all residual acidity, and R1 is an adipic acidresidue.

10. A water-soluble ester, as defined in claim 1, wherein alloccurrences of n are 0, n represents the numeral 2, m represents anumeral varying from '7 to 11, and the high molal 'acyl radical which ispart of R2 is a ricinoleic acid residue,

the ratio of p to .p is 2v to 1 with added neu tralization of allresidual acidity, and-R1 is a succinic acid residue.

11. A water-soluble ester, as defined in claim 1, wherein alloccurrences of n are 0, n represents the numeral 2, m represents anumeral, varying from 7 to 11, and the high molal acyl radical which ispart of R2 is a ricinoleic acid residue,

' (A) Esterifying a polyalkylene glycol having'at least 7 and not morethan 1'1 ether linkages, and the alkylene radical thereof containing atleast 2 and not more than 6 carbon atoms, with a polybasic carboxy acidhaving not more than 6 carbon atoms in the predetermined ratio of morethan 1 and not more than 2 moles of the polybasic acid for each mole ofthe glycolto',

produce a water-soluble product; and (B) Esterifying 1 molal proportionof said alkylene glycol dihydrogen acid ester with 2 moles of ahydroxylated acylated amide

